DE60024807T2 - Solvates of pymetrozine - Google Patents

Description

The The present invention relates to novel, insecticidally-active, defined solvates of pymetrozine, a method of preparation of these compounds, compositions containing these compounds, a process for producing these compositions, a process for pest control with These compositions and their use for controlling Animal pests, especially of insects and members of the order of Acarina, especially in fruits of crops.

Several Solvates of a chemical compound, such as hydrates, can have very different physical properties, the to unpredictable problems during the technical production and processing of these compounds to lead can. The properties of such solvates often have a decisive influence on the separability (Filtration), stirrability (Crystal volume), surface activity (foaming), Drying rate, solubility, Quality, Formulating ability and storage stability (eg, hygroscopy) of, for example, pesticidal compounds. For example, you can the grinding and formulation properties as well as the handling of such pesticide mixtures depending on the particular solvation completely differ. Because in the different stages of the synthesis of a Manufacturing process different physical properties important to the respective synthesis products, it is particularly advantageous the for the respective phase of the synthesis optimally suitable solvation form to find.

pymetrozine is known for example from US-P-4931439, wherein the preparation in Example P3. However, from this example can not be assumed that the solvated product obtained with ethanol, diethyl ether or water even though the product was made with ethanol during production, Diethyl ether and water had come into contact. At the end of the manufacturing process the compound was dried and was used in the formulation examples used as a substantially anhydrous and solvent-free product. The physical parameters, such as temperature, humidity and pressure, in the special production of certain solvents are crucial, are nowhere in the above patent specification specified.

object It is therefore an object of the present invention to provide solvates, especially hydrates, and to prepare salts of these solvates of pymetrozine, the Properties mentioned above Show advantages, especially in the production and handling of Pesticide mixtures, especially granules.

wobei s 2 ist,
in freier Form oder in Salzform; und ihre Tautomere, jeweils in freier Form oder in Salzform, ein Verfahren zur Herstellung und Verwendung dieser Verbindungen, ihrer Salze und deren Tautomere; Pestizide, deren aktiver Bestandteil aus diesen Verbindungen und ihren Tautomeren ausgewählt ist; und ein Verfahren zur Herstellung dieser Solvate und, sofern zutreffend, ihrer Salze, ein Verfahren zur Herstellung dieser Zusammensetzungen und ihre Verwendung.Thus, the present invention relates to compounds of the formula:

where s is 2,
in free form or in salt form; and their tautomers, each in free form or in salt form, a process for the preparation and use of these compounds, their salts and their tautomers; Pesticides whose active ingredient is selected from these compounds and their tautomers; and a process for the preparation of these solvates and, if applicable, their salts, a process for the preparation of these compositions and their use.

in the The following is between the compound of formula (I) or salts of which r and s are not 0 at the same time, and pymetrozine, which is the solvate-free compound (where r and s are simultaneously 0 are).

The compounds of formula (I) have several basic centers. They can therefore form acid addition salts. These are, for example, with strong inorganic acids such as mineral acids, eg. Perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or a hydrohalic acid; with strong organic carboxylic acids, such as C ₁ -C ₄ -alkanecarboxylic acids, optionally substituted z. B. with halogen, for. As acetic acid, such as optionally unsaturated dicarboxylic acids, eg. Oxalic, malonic, Succinic, maleic, fumaric or phthalic acid, such as hydroxycarboxylic acids, eg. As ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid; or with organic sulfonic acids, such as C ₁ -C ₄ -alkanesulfonic or arylsulfonic acids, optionally substituted, for. B. with halogen, for. For example, methanesulfonic or p-toluenesulfonic acid formed. In addition, the compounds of formula (I) can form salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali or alkaline earth metal salts, for. For example, sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, z. For example, ethyl, diethyl, triethyl or dimethylpropylamine, or a mono-, di- or trihydroxy-lower alkylamine, for. As mono-, di- or triethanolamine.

In In this case, on the one hand, salts with formic acid, acetic acid and lactic acid are preferred, and on the other hand are the sodium, potassium, magnesium and calcium salts preferred, especially sodium salts. On the other hand, the same is the connection of the formula (I) in free form, d. H. in which r is 0, preferred.

The Compounds (I) also have an acid group and therefore can Form salts with bases. Suitable salts with bases are, for example Metal salts, including Metal complexes, such as alkali metal or alkaline earth metal salts, e.g. As sodium, potassium or magnesium salts, but also complex salts with, for example, copper, nickel or iron; or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. Ethyl, diethyl, Triethyl or dimethylpropylamine, or a mono-, di- or trihydroxy-lower alkylamine, z. As mono-, di- or triethanolamine. If necessary, the corresponding internal salts are formed. Agrochemically advantageous Salts are preferred in the context of this invention. As above and described below, it can be assumed that the compounds (I) in free form comprise the corresponding salts and that the salts comprising the free compounds (I). In any case, the free Shape generally preferred.

A particularly preferred object of the invention is a compound of formula (I) in which r is 0 and s is 2 (pymetrozinedihydrate) and which exhibits the reflections listed in Table 1 in the powder diagram. Table 1: Powder data of the pymetrozine dihydrate there) intensity 12.4 average 7.1 weak 6.8 very strong 6.3 weak 6.2 average 5.82 very weak 5.40 average 5.14 very weak 4.85 weak 4.68 very weak 4.52 very weak 4.31 very weak 4.14 weak 4.08 very weak 3.96 very weak 3.83 very weak 3.71 very weak 3.58 weak 3.47 very strong 3.44 very strong 3.25 strongly 3.21 weak 3.09 average 3.03 weak 2.99 weak 2.90 weak 2.82 weak 2.76 weak 2.57 weak

The powder data of the known α-modification of pymetrozine are also given below for comparison: TABLE 2 Powder data of the pymetrozine α-modification there) intensity 11.9 weak 9.7 average 7.6 average 6.4 very weak 6.1 average 5.95 average 5.65 average 5.26 average 4.76 weak 4.49 weak 4.43 very weak 4.37 weak 4.11 strongly 3.99 very strong 3.81 weak 3.57 weak 3.52 weak 3.48 strongly 3.34 very strong 3.26 very weak 3.14 strongly 3.07 very weak 2.99 average 2.90 weak 2.82 average 2.80 weak 2.75 weak 2.66 very weak 2.61 weak

The Measurement of the powder data diagrams was done with an X'Pert powder diffractometer (Philips) with the TTK camera (Anton Paar), using Copper radiation (λ = 1.54060 Å), carried out. The measurement of dihydrate from Table 1 was at room temperature carried out.

It is now surprisingly been shown that dried, water- and solvent-free pymetrozine is capable of reversibly removing water or solvent from the atmosphere or while mixing or grinding. It was found that at Room temperature and relative humidity less than 10 % Water-containing pymetrozine completely releases water and at a relative Moisture between 60% and 70% about 16 to 17 wt .-% water resumes. The above-described water content of 16 to 17 % By weight agrees very well with a dihydrate.

Even those pesticide compositions that are water- and solvent-free Contain pymetrozine, usually take Water or the corresponding solvent from the atmosphere when left under a sufficiently high vapor pressure become. This solvation, especially the water absorption, of Formulations, especially of water-dispersible powders and granules, especially granules, can cause handling and storage problems lead pesticide compositions, but these problems do not occur when pymetrozine in the form of a defined solvates either during the manufacturing process of the pesticidal composition is added or in a suitable manner during of the aforementioned Manufacturing process is produced. For example, such must Formulations no longer in airtight containers be stored and once the containers have been opened, have to They will not be resealed tightly, hence the quality of the goods preserved.

In addition, the preparation of the relatively high water content formulation of the invention is simpler than the preparation of substantially anhydrous formulations or when the α modification is used, since the production is generally influenced in such a way that water is added to the formulation step and consequently has to be removed again. The complete or almost complete removal of the water involves considerable disadvantages, such as high energy consumption, longer production times, increased equipment consumption, etc.

A Ready-to-use formulation of pymetrozine with a water content of about 10% by weight under normal conditions is only marginally Absorb moisture from the air, whereas a formulation, their water content during the production has been reduced to less than 5% or at the Beginning of production used essentially anhydrous ingredients are very hygroscopic. The long-term storage of formulations having a water content of less than about 5% by weight requires one Packaging that completely sealed against water vapor and using appropriately higher Effort must be made. When disposing of this packaging causes greater problems than conventional, not completely waterproof containers.

Besides, they are Packaging whose contents can not be used up immediately generally not sufficiently resealable waterproof. It is therefore inevitable that water absorbed by the anhydrous formulation.

If An anhydrous formulation absorbs water, its quality is within a period of weeks to months significantly reduced. This means that the official statements regarding the ratio of the active substance in the formulation is no longer observed under certain circumstances can be. Therefore, the water absorption by an anhydrous formulation to unsealable Lead goods, if stored by the manufacturer or retailer, without that yourself the active ingredient actually decomposed.

Spontaneity: The quality of a water-dispersible granules is significantly enhanced by its User friendliness determined. Consequently, the user expects that to happen Granules within a few minutes after mixing the spray solution completely in his primary particles decomposed. When formulating pymetrozine this property, as spontaneity is known, not obtained when a formulation is used, the original is anhydrous or has a low water content, but during the Storage has taken up water again. Contrary to the essential Anhydrous formulations show the formulations according to the invention after storage over a period of 7 days in a suitable test device a complete Decomposition of the granules into their primary particles within less Minutes.

Table 3: Comparison of spontaneity after different periods (test carried out analogously to CIPAC MT 174); Pymetrozing granules with an active substance content of 50% by weight

At the Measuring spontaneity go through the spray solution first shake the composition in a cylinder in the presence of a specific Amount of water produced. After 0.5 to 1 min, 90% of the solution is removed by suction, and the remaining solution is concentrated by evaporation. The residue obtained is checked after drying, and the amount of the original used material suspended in the solution calculated in%.

Without consideration of the water content, the granules have a composition according to the following Example F10 and are prepared as indicated therein.

Further Advantages of these formulations according to the claim of the present Invention are an improved suspension ability in the spray solution and improved dispersibility.

One desired Solvate may be prepared before combining the active ingredient with the formulation carriers or alternatively during the formulation preparation by suitably contacting the active ingredient with the desired Amount of water to be produced. It is thus possible to use different methods for the specific production of these hydrates and pesticidal compositions, which contain water to use. Anhydrous pymetrozine can for example, in a mixer in an atmosphere with a defined water content until you get the desired Form stirred or ground. Or it becomes pymetrozine with high water content, which results from the manufacturing process or by mixing of essentially anhydrous pymetrozine, especially with one huge Amount of water has been produced in a dryer to desired Dried water content. This process for producing a defined hydrate from pymetrozine therefore form a further subject of the present invention Invention.

suitable Formulations for the compounds of the formula (I) are described, for example, in USP 4931439. They are all characterized by the absence of pymetrozine in solvated form contain.

The Formulations, d. H. Means, preparations or compositions containing an active ingredient of the formula (I) and a or more solid or liquid Formulation excipients contained, also form an object of this invention. she For example, in a known manner by intimate Mixing and / or grinding of the active ingredient of the formula (I) with the Formulation excipients, such as solvates or solid carriers, produced. An alternative, new manufacturing process, which in a similar way Way forms an object of this invention, consists of Adding the solvating agent during the formulation process, whereby during the formulation process, the solvate is formed. In an important Variant of this method, the solvating agent can be added excessively be removed at the end, for example by evaporation again become, whereby the desired Value is obtained. For certain mixtures, this procedure may significantly simplify the manufacturing process. The corresponding Compositions produced by this process form in similar Way an object of this invention.

surfactants Compounds (surfactants) can Furthermore used to prepare the formulations. Examples of Solvates and solid carriers be z. In US-P-4931439. Dependent on the nature of the active compound of the formula (I) to be formulated are suitable surface-active compounds nonionic, cationic and / or anionic surfactants and surfactant mixtures with good dispersing and spritzing properties. Examples of suitable For example, anionic, nonionic and cationic surfactants in US Pat. No. 4,931,439.

The insecticides according to the invention and acaricidal formulations are usually from 0.1 to 99 Wt .-%, in particular from 1 to 95 wt .-% of the compound of formula (I), from 1 to 99.9 wt .-%, in particular from 5 to 99.8 wt .-% of a solid or liquid Formulation excipient, and from 0 to 25 wt .-%, in particular from 0.1 to 25 wt .-% of a Surfactants, included. equally insecticidal and acaricidal formulations are preferred From 0.1 to 94% by weight, in particular from 0.1 to 90% by weight, of pymetrozine, from 5 to 30% by weight of a solvating agent, from 1 to 94.9 Wt .-%, in particular from 5 to 90 wt .-% of a solid or liquid formulation carrier and from 0 to 30 wt .-%, in particular from 0.1 to 25 wt .-% of a Containing surfactants.

Especially preferred pesticide formulations, especially granules, are those containing from 3 to 5% by weight of pymetrozine or those containing from 30 to 50 wt .-% Pyme trozin. Equally preferred are water-dispersible powders containing from 25 to 50% by weight of pymetrozine contain.

As well preferred are pesticide formulations, in particular granules, the from 8 to 40% by weight, preferably from 8 to 20% by weight, in particular from 8 to 14 wt .-% water. Equally preferred are pesticide formulations, in particular granules containing from 40 to 60 wt .-% pymetrozine, in particular 50 wt .-% pymetrozine.

As well preferred are spray powders which are from 6 to 20 wt .-%, in particular from 8 to 12% by weight of water and from 20 to 30% by weight of pymetrozine, in particular 25 wt .-% pymetrozine.

When specifying the amount of water content, the fact that the formulation vehicles themselves often have some residual water content should be taken into account. For this reason, the actually determined water content of the formulations is generally slightly higher than that calculated from the hydrate composition. In general, the measured content is about 1 to 5 wt .-% above the calculated. As described above and below, it is believed that a substantially anhydrous or low water content pymetrozine formulation is a mixture of pesticides containing at most 6% by weight of water based on the total mixture.

Even though it is preferred to formulate commercial products as concentrates, the end user will normally use diluted formulations. The compositions can also contain other ingredients such as stabilizers, for example where appropriate epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), Activators, antifoams, typically silicone oil, preservatives, viscosity regulators, Binders, tackifiers and fertilizers or other active substances.

The Compounds of formula (I) are usually applied to plants or their Locations in concentrations of 0.001 to 1.0 kg / ha, preferably 0.1 to 0.6 kg / ha applied. The required for the desired effect Concentration can be determined experimentally. She is from the Type of action, the stage of development of the crop and the pest and depend on the application (locus, time, method) and may vary widely as a result of these variables. As in The nature of the compositions will be the modes of administration, such as spraying, Atomize, pollinate, Wetting, sprinkling or pouring, according to the intended Goals and the prevailing circumstances.

The Compositions containing the compounds of formula (I), have excellent insecticidal properties and are suitable thus for the application with fruits of crops, in particular cereals, cotton, soybeans, sugar beets, Sugarcane, plantations, rapeseed, corn and rice. It will be like that too assumed that fruits such fruit are by conventional breeding or genetic engineering techniques have been made resistant to pesticides. pests especially insects and members of the order of Acarina, the with the formulations according to the invention fought can be are described for example in US-P-931439 and US-P-46145.

The The invention is illustrated by the following non-limiting examples.

formulation Examples

% refers to weight percentages.

Example F1:

emulsions with every desired Can concentrate made from these concentrates by dilution with water become.

Example F2:

Example F3:

The solutions are suitable for the use in the form of microdrops.

Example F4:

Of the Active ingredient is suspended in polyethylene glycol 300, on the carrier sprayed, and the granules are then mixed with the silica ground.

Example F5:

Ready dusts be by intimately mixing the excipients with the drug and subsequent Grind received.

Example F6:

The Compounds are mixed with the additives, and the mixture will be in a suitable mill milled, thereby obtaining wettable powders which are diluted with water can, whereby suspensions of the respective desired concentration are obtained become.

Example F7:

The active ingredient is mixed with the additives and ground, and the mixture is moistened with water. The mixture is extruded, granulated and then dried in a stream of air. Example F8: suspension concentrate Pymetrozindihydrat 40% propylene glycol 5% Nonylphenol polyethylene glycol ether (15 moles EO) 6% Tristyrylphenolpolyglykoletherphosphattriethanolamin 7% heteropolysaccharide 1 % 1,2-benzisothiazol-3-one 0.2% Silicone oil in the form of a 75% aqueous emulsion 0.8% water 40%

Of the finely ground active substance is intimately mixed with the additives. In this way, a suspension concentrate is obtained, from which the suspensions of the respectively desired Concentration by dilution can be made with water.

Example F9: Production a water-dispersible granule of the compound of the formula (I):

The following substances are mixed and then ground in a conventional mill: 60% anhydrous pymetrozine 5% Natriumdibutylnaphthalensulfonat 10% sodium ligninsulfonate 5% sodium sulphate 15% polymeric organic carrier 0.1% Perfluoralkylphosphorsäure 4.9% silica

The Mixture is subsequently with 35-45 Wt .-% water mixed and granulated. After drying up to a residual moisture of 8-12 % on a commercial continuous dryer, the granules obtained up to defined grain size sieved. Granules are obtained which are the compound of formula (I) in hydrated form.

Example F10: Production a water-dispersible granule of the compound of the formula (I):

The following substances are mixed 50% anhydrous pymetrozine 5% Natriumdibutylnaphthalensulfonat 10% sodium ligninsulfonate 5% sodium sulphate 15% polymeric organic carrier 0.1% Perfluoralkylphosphorsäure remaining% silica

The Mixture is subsequently mixed with 50 to 70 wt .-% water and granulated. After drying up to a residual moisture of 8-12 % on a commercial continuous dryer, the granules obtained up to defined grain size sieved. Granules are obtained which contain the compound of the formula (I) contained in hydrated form.

Preparation Examples of solvates of the formula (I) and of formulations containing these solvates contain:

Example P1: Preparation the compound of formula (I) wherein r is 0 and s 2 (dihydrate of Pymetrozine):

pymetrozine is 10 days in a sealed container with a controlled the atmosphere stored at 89% relative humidity. The product will then be from the container taken and equilibrated in a laboratory atmosphere. On a heat scale the product obtained shows a weight loss between room temperature and 125 ° C of 13.9%, giving two water molecules corresponds to (theoretical loss 14.2%).

In the X-ray diffractometer For example, the pattern reproduced in Table 1 was made using copper radiation (λ 1.54060Å) at room temperature found.

Example P2: Preparation the compound of formula (I) wherein r is 0 and s is 2 (dihydrate of Pymetrozine):

In A mixer is given a defined amount of water (16% based on anhydrous pymetrozine) evenly the active ingredient under cooling sprayed, and the powder is then added slowly until it cools down stirred to room temperature.

Example P3: Preparation the compound of formula (I) wherein r is 0 and s is 2 (dihydrate of Pymetrozine):

In A fast mixer is a defined amount of water evenly a mixture of the active ingredient and the excipients sprayed, and after storage, the powder becomes the final formulation further processed.

Example P4: Production the compound of formula (I) wherein r is 0 and s is 2 (dihydrate of Pymetrozine):

In a stirred tank is pymetrozine in the presence of the remaining formulation components suspended in water, and the mixture is then poured into sprayed a stream of air finely and dried to a residual moisture of 6-15%.

Example P5:

0.5 g of pymetrozine are stirred for 9 days at 25 ° C in 2.5 g of water, whereupon the suspension is filtered. The dihydrate used in thermogravimetry a weight loss of 12% by weight is obtained.

Claims (6)

Compound of the formula

in substantially pure form, where s is 2; and wherein the compound is in free form or in salt form, and the tautomers thereof each in free form or in salt form. A process for the preparation of a compound of the formula (I) according to claim 1, wherein a non-solvated, pesticidally active compound of the formula

is brought into contact with water. A process for the preparation of a pesticidal composition comprising a compound of claim 1 of formula (I) and one or more additives which comprises intimately mixing or grinding a substantially solvate-free compound of formula

together with the formulation vehicles and water. Process for the preparation of a pesticidal composition, which is a compound according to claim 1 of formula (I) and one or contains several additives, which is the intimate mixing or grinding of the active ingredient of the formula (I) with the formulation vehicles includes. A process for the preparation of a pesticidal composition comprising a compound of claim 1 of formula (I) and one or more additives which comprises contacting a pesticidal mixture containing a substantially solvate-free compound of the formula

and one or more additives, with an excess of water, and the water is finally removed by evaporation, for example. Pesticide composition containing a compound of Formula (I) according to claim 1 and one or more additives.